The present invention relates to a process for inhibiting the re-absorption of migrating dyes in the wash liquor.
It is well known that various metal compounds, e.g. manganese complexes, are useful in detergents as catalysts for oxidation with peroxygen compounds such as perborate or peroxides. It is also known that certain other manganese complexes cause enhanced bleaching effects on dirt or dyes in the wash bath. Moreover, these manganese complexes do not exhaust at all on to cotton, polyamide or polyester fibres so that the complexes cannot lead to fibre discolouration problems.
One problem associated with the evaluation of a compound as a candidate for use in a process for inhibiting the re-absorption of migrating dyes in the wash liquor, is the lack of a sufficiently reliable and comprehensive screening technique. Such a technique has now been developed and used to quantify the dye transfer inhibition performance of potential substances. This screening procedure comprises a variety of tests which makes it possible to determine the usefulness/damage balance of any candidates on a quantitative basis. A product is characterised in terms of its specific effectivity, scope of use, compatibility with the most important system components, oxygen demand and its fibre- and dyestuff degradation potential. Moreover, the precision of the data is such that structure/effect relationships can be developed. The application of the new evaluation technique to manganese complexes has resulted in the identification of further manganese complexes which exhibit excellent performance as dye transfer inhibitors, which are of relatively low molecular weight and the effectiveness of which is substantial even at low levels of addition.
Accordingly, the present invention provides a process for inhibiting the re-absorption of migrating dyes in the wash liquor, comprising introducing into a wash liquor containing a peroxide-containing detergent, from 0.5 to 150, preferably from 1.5 to 75, especially from 7.5 to 40 mg, per liter of wash liquor, of one or more compounds having the formula: 
in which n is 1, 2 or 3;
A is an anion;
R1 is hydrogen or C1-C4-alkyl,
Y is linear or branched alkylene of the formula xe2x80x94[C(R1)2]m in which m is an integer ranging from 1 to 8 and each R1 independently from the other has its previous significance; xe2x80x94CXxe2x95x90CXxe2x80x94 in which X is cyano, linear or branched C1-C8-alkyl or di(linear or branched C1-C8-alkyl-amino;
xe2x80x94(CH2)qxe2x80x94NR1xe2x80x94(CH2)qxe2x80x94 in which R1 has its previous significance and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenylene residue having the formula: 
in which R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine,
R and Rxe2x80x2 are each independently from the other cyano; halogen; hydroxy; OR1 or COOR1 in which R1 has its previous significance; nitro; linear or branched partially or completely fluorinated C1-C8-alkyl; NR3R4 in which R3 and R4 are the same or different and each is hydrogen or linear or branched C1-C12-alkyl; xe2x80x94N⊕R1R3R4 in which R1, R3 and R4 have their previous significance or linear or branched C1-C8-alkylene-R2 in which R2 is OR1, COOR1 or NR3R4,
R5 and R6 are each independently from the other hydrogen; linear or branched C1-C4-alkyl; unsubstituted aryl or aryl which is substituted by cyano, halogen, OR1 or COOR1, nitro, linear or branched C1-C8-alkyl, NR3R4 in which R3 and R4 are the same or different and each is hydrogen or linear or branched C1-C12-alkyl; xe2x80x94N⊕R1R3R4 in which R1, R3 and R4 have their previous significance or linear or branched C1-C8-alkylene-R2 in which R2 is OR1, COOR1 or NR3R4,
with the proviso that each n is 1, if R and Rxe2x80x2 are both C1-C4-alkyl.
When Y is a 1,2-cyclohexylene residue, this residue may be in any of its cis/trans stereoisomeric forms.
Y is preferably xe2x80x94[C(R8)2]2 wherein R8 is hydrogen or methyl, xe2x80x94CXxe2x95x90CXxe2x80x94 in which X is cyano, xe2x80x94(CH2)qxe2x80x94NR8xe2x80x94(CH2)qxe2x80x94 in which R8 has its previous significance and q is 1,2,3 or 4; or a 1,2-cyclohexylene or phenylene residue having the formula: 
Preferred halogen atoms R or Rxe2x80x2 are chlorine, bromine and fluorine atoms.
When n is 1, preferably the group R or Rxe2x80x2 respectively is in the 4-position of the respective benzene ring, with the exceptions that when R or Rxe2x80x2 is nitro or CO2R2, the group R or Rxe2x80x2 is preferably in the 5-position of the respective benzene ring. When n is 2, preferably the groups R or Rxe2x80x2 are in the 4,6-positions of the respective benzene ring, with the exceptions that when R or Rxe2x80x2 is nitro or CO2R2 the groups R or Rxe2x80x2 are preferably in the 3,5-positions of the respective benzene ring.
When R or Rxe2x80x2 is the group di-(C1-C12alkyl)amino, the alkyl moiety may be a straight- or branched chain alkyl moiety, and it preferably contains from 1 to 8, more preferably from 1 to 4 and, especially, 1 or 2 carbon atoms.
Preferred groups R and Rxe2x80x2 are dimethylamino, diethylamino, hydroxy, methoxy, ethoxy, chloro or nitro.
Anions A include halide, especially chloride, perchlorate, sulphate, nitrate, hydroxide, BF4xe2x88x92, PF6xe2x88x92, carboxylate, especially acetate, triflate or tosylate.
Some of the compounds of formula (1) and the ligands from which they are derived are known compounds. For example, in U.S. Pat. No. 5,281,578 there is described the preparation of N,N-bis(4-dimethylaminosalicylidene)diiminoethylene; in EP-A-0 693 550 there is disclosed the production of the manganese complex of N,N-bis(4-diethylaminosalicylidene)diiminoethylene; and in Bernado et.al., Inorg. Chem. 35 (2) 387 (1996), there is disclosed the production of N,N-bis(4-diethylaminosalicylidene)diiminocyclohexylene as well as the production of the manganese complex N,N-bis(4-diethylaminosalicylidene)diiminocyclohexylene. New compounds of formula (1) and new ligands from which they are derived form further aspects of the present invention.
Moreover, the use, as dye transfer inhibitors, of those compounds of formula (1) in which A is an anion and a) Y is xe2x80x94CH2CH2xe2x80x94 each R is di-(C1-C2alkyl)amino; or b) Y is cyclohexylene and each R is di-(C1-C2alkyl)amino has been broadly indicated, but not specifically described, in GB-A-2,296,015. On the other hand, the use, as dye transfer inhibitors, of those compounds of formula (1) in which A is an anion, Y is xe2x80x94CH2CH2xe2x80x94 and each R is hydroxy, is believed to be completely new.
Of particular interest for use in in the method of the present invention are those compounds of formulae: 
The present invention also provides a detergent composition comprising:
i) 5-90%, preferably 5-70% of A) an anionic surfactant and/or B) a nonionic surfactant;
ii) 5-70%, preferably 5-50%, especially 5-40% of C) a builder;
iii) 0.1-30%, preferably 1-12% of D) a peroxide; and
iv) 0.005-2%, preferably 0.02-1%, especially 0.1-0.5% of E) a compound of formula (1) or (2) as defined above, each by weight, based on the total weight of the detergent.
The detergent may be formulated as a solid; or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt. % of water, and based on a suspension of a builder in a non-ionic surfactant, as described, e.g., in GB-A-2158454.
Preferably, the detergent is in powder or granulate form.
Such powder or granulate forms may be produced by firstly forming a base powder by spray-drying an aqueous slurry containing all the said components, apart from the components D) and E); then adding the components D) and E) by dry-blending them into the base powder. In a further process, the component E) may be added to an aqueous slurry containing components A), B) and C), followed by spray-drying the slurry prior to dry-blending component D) into the mixture. In a still further process, component B) is not present, or is only partly present in an aqueous slurry containing components A) and C); component E) is incorporated into component B), which is then added to the spray-dried base powder; and finally component D) is dry-blended into the mixture.
The anionic surfactant component A) may be, e.g., a sulphate, sulphonate or carboxylate surfactant, or a mixture of these. Preferred sulphates are alkyl sulphates having 12-22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxy sulphates having 10-20 carbon atoms in the alkyl radical.
Preferred sulphonates include alkyl benzene sulphonates having 9-15 carbon atoms in the alkyl radical.
In each case, the cation is preferably an alkali metal, especially sodium.
Preferred carboxylates are alkali metal sarcosinates of formula Rxe2x80x94COxe2x80x94N(R1)xe2x80x94CH2COOM1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R1 is hydrogen or C1-C4 alkyl and M1 is alkali metal.
The nonionic surfactant component B) may be, e.g., a condensate of ethylene oxide with a C9-C15 primary alcohol having 3-8 moles of ethylene oxide per mole.
The builder component C) may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.
Preferred silicates are crystalline layered sodium silicates of the formula NaHSimO2m+1.pH2O or Na2SimO2m+1.pH2O in which m is a number from 1.9 to 4 and p is 0 to 20.
Preferred aluminosilicates are the commercially-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.
Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.
Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid, ethylenediaminedisuccinate in racemic form as well as the enantiomeric S,S-form
Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
The peroxide component D) may be any organic or inorganic peroxide compound, described in the literature or available on the market, which bleaches textiles at conventional washing temperatures, e.g. temperatures in the range of from 30xc2x0 C. to 90xc2x0 C. In particular, the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest. It is preferred, however, to employ very active inorganic peroxides, such as persulphate, perborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides. Peroxides can have different crystalline forms and/or different degrees of hydration. They may be used in admixture with other organic or inorganic salts, thereby improving their stability to storage.
The addition of the peroxides to the detergent is effected, in particular, by mixing the components, for example by means of screw-metering systems and/or fluidized bed mixers.
The detergents may contain, in addition to the combination according to the invention, one or more of fluorescent whitening agents, such as a bis-triazinylamino-stilbene-disulphonic acid, a bis-triazolyl-stilbene-disulphonic add, a bis-styryl-biphenyl, a bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, a bis-benzimidazolyl derivative, a coumarine derivative or a pyrazoline derivative; soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; enzymes, such as amylases; photobleaching agents; pigments; and/or shading agents. These constituents should, of course, be stable to the bleaching system employed.
A particularly preferred detergent co-additive is a polymer known to be useful in preventing the transfer of labile dyes between fabrics during the washing cycle. Preferred examples of such polymers are polyvinyl pyrrolidones, optionally modified by the inclusion of an anionic or cationic substituent, especially those having a molecular weight in the range from 5000 to 60,000, in particular from 10,00 to 50,000. Preferably, such polymer is used in an amount ranging from 0.05 to 5%, preferably 0.2-1.7% by weight, based on the weight of the detergent.
The detergents may additionally contain so-called perborate-activators, e.g. TAGU or, preferably TAED. This is preferably used in an amount of 0.05 through 5% by weight, especially 0.2 through 1.7% by weight, relative to the total weight of the detergent.
The manganese complexes of formula (2) are new compounds and some of the manganese complexes of formula (1) are new too.
The invention consequently also relates to manganese complexes of formula (3) or of formula (2) 
in which n is 1, 2 or 3;
A is an anion;
R and Rxe2x80x2 are each independently from the other cyano; halogen; hydroxy; OR1 or COOR1 in which R1 has its previous significance; nitro; linear or branched partially or completely fluorinated C1-C8-alkyl; NR3R4 in which R3 and R4 are the same or different and each is hydrogen or linear or branched C1-C12-alkyl; xe2x80x94N⊕R1R3R4 in which R1, R3 and R4 have their previous significance or linear or branched C1-C8-alkylene-R2 in which R2 is OR1, COOR1 or NR3R4,
R1 is hydrogen or C1-C4-alkyl,
Y1 is xe2x80x94CXxe2x95x90CXxe2x80x94 in which X is cyano, xe2x80x94(CH2)qxe2x80x94NR1xe2x80x94(CH2)qxe2x80x94 in which R1 has its previous significance and q is 1, 2, 3 or 4; linear or branched alkylene of the formula xe2x80x94[C(R1)2]m in which m is an integer ranging from 1 to 8 and each R1 independently from the other has its previous significance, with the proviso that at least one R1 is C1-C4-alkyl; or a 1,2-cyclohexylene or phenylene residue having the formula: 
in which R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, with the proviso that each n is 1 if R and Rxe2x80x2 are both C1-C4-alkyl and Y1 is an unsubstituted 1,2-cyclohexylene residue,
Y is linear or branched alkylene of the formula xe2x80x94[C(R1)2]m in which m is an integer ranging from 1 to 8 and each R1 independently from the other has its previous significance; xe2x80x94CXxe2x95x90CXxe2x80x94 in which X is cyano, linear or branched C1-C8-alkyl or di(linear or branched C1-C8-alkyl)amino;
xe2x80x94(CH2)qxe2x80x94NR1xe2x80x94(CH2)qxe2x80x94 in which R1 has its previous significance and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenylene residue having the formula: 
in which R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine,
R5 and R6 are each independently from the other hydrogen; linear or branched C1-C4-alkyl; unsubstituted aryl or aryl which is substituted by cyano, halogen, OR1 or COOR1, nitro, linear or branched C1-C8-alkyl, NR3R4 in which R3 and R4 are the same or different and each is hydrogen or linear or branched C1-C12-alkyl; xe2x80x94N⊕R1R3R4 in which R1, R3 and R4 have their previous significance or linear or branched C1-C8-alkylene-R2 in which R2 is OR1, COOR1 or NR3R4.
The ligands of formulae (4) or (5) which are contained in the manganese complexes are new themselves and these ligands are also part of the instant invention. The invention consequently also relates to compounds of the formula (4) or of formula (5) 
in which n is 1, 2 or 3;
R and Rxe2x80x2 are each independently from the other cyano; halogen; hydroxy; OR1 or COOR1 in which R1 has its previous significance; nitro; linear or branched partially or completely fluorinated C1-C8-alkyl; NR3R4 in which R3 and R4 are the same or different and each is hydrogen or linear or branched C1-C12-alkyl; xe2x80x94N⊕R1R3R4 in which R1, R3 and R4 have their previous significance or linear or branched C1-C8-alkylene-R2 in which R2 is OR1, COOR1 or NR3R4,
R1 is hydrogen or C1-C4-alkyl,
Y1 is xe2x80x94CXxe2x95x90CXxe2x80x94 in which X is cyano, xe2x80x94(CH2)qxe2x80x94NR1xe2x80x94(CH2)qxe2x80x94 in which R1 has its previous significance and q is 1, 2, 3 or 4; linear or branched alkylene of the formula xe2x80x94[C(R1)2]m in which m is an integer ranging from 1 to 8 and each R1 independently from the other has its previous significance, with the proviso that at least one R1 is C1-C4-alkyl; or a 1,2-cyclohexylene or phenylene residue having the formula: 
in which R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, with the proviso that each n is 1 if R and Rxe2x80x2 are both C1C4-alkyl and Y1 is an unsubstituted 1,2-cyclohexylene residue,
Y is linear or branched alkylene of the formula xe2x80x94[C(R1)2]m in which m is an integer ranging from 1 to 8 and each R1 independently from the other has its previous significance; xe2x80x94CXxe2x95x90CXxe2x80x94 in which X is cyano, linear or branched C1-C8-alkyl or di(linear or branched C1-C8-alkyl)-amino;
xe2x80x94(CH2)qxe2x80x94NR1xe2x80x94(CH2)qxe2x80x94 in which R1 has its previous significance and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenylene residue having the formula: 
in which R7 is hydrogen, CH2OH or CH2NH2 or SO3M, where M is hydrogen, an alkali metal atom, ammonium or a cation formed from an amine,
R5 and R6 are each independently from the other hydrogen; linear or branched C1-C4-alkyl; unsubstituted aryl or aryl which is substituted by cyano, halogen, OR1 or COOR1, nitro, linear or branched C1-C8-alkyl, NR3R4 in which R3 and R4 are the same or different and each is hydrogen or linear or branched C1-C12-alkyl; xe2x80x94N⊕R1R3R4 in which R1, R3 and R4 have their previous significance or linear or branched C1-C8-alkylene-R2 in which R2 is OR1, COOR1 or NR3R4.
Preferred compounds of formula (4) are the following: 
Preferred compounds of formula (5) are 
The following Examples serve to illustrate the invention; parts and percentages are by weight, unless otherwise stated.
Preparation of the New Ligands
Ligand 2a
a) Preparation of the Corresponding Aldehyde
Firstly, the starting compound N,N-dibutyl-4-amino-2-hydroxy-benzaldehyde had to be prepared by Vilsmeyer formylation of N,N-dibutyl-3-amino-phenol. The Vilsmeyer reagent was prepared by slow addition of 4.7 ml (0.0497 mol) of phosphorus oxychloride to 15 ml (0.189 mol) of N,N-dimethyl formamide with stirring for 15 minutes at room temperature. Stirring was continued for 30 more minutes before this Vilsmeyer reagent was used. 11 g (0.497 mol) N,N-dibutyl-3-amino-phenol, prepared by alkylation of 3-aminophenol after the procedure described in EP 0356173 was dissolved in 13 ml N,N-dimethyl formamide. This solution was added dropwise at room temperature to the Vilsmeyer reagent described above. The solution was stirred for 3 h, heated to 50xc2x0 C. for 10 minutes. The solution was cooled to room temperature and stirred for another 2 h. Then, the reaction mixture was poured onto 70 g ice and stirred for 1 h. The aequous layer was extracted three times with 100 ml chloroform. The combined organic layers were evaporated in vacuo. The raw product was purified by column chromatography (450 g silicagel, eluent hexane/ethyl acetate 15:1, vol. ratio). 3.2 g (26%) N,N-Dibutylamino-2-hydroxy-benzaldehyde was obtained as an orange oily compound.
b) Preparation of the Ligand 2a
To a solution of 1 g (0.004 mol) 4 N,N-dibutyl-4-amino-2-hydroxy-benzaldehyde in 2 ml ethanol at 55xc2x0 C. were added dropwise 0.13 ml (0.00191 mol) of ethylene diamine. The resulting clear solution was kept under stirring for 4 h between 60-65xc2x0 C. The solution was cooled and the precipitate formed was filtered and dried to give 540 mg (54%) of a slightly brownish solid.
13C NMR (CDCl3): xcex4=14.0 (aliph. CH3), 20.2, 29.5, 50.8, 58.2 (aliph. CH2), 98.2, 103.1, 132.9 (tert. Aryl-C), 108.2, 151.9, 165.7 (quart Aryl-C), 164.3 (Cxe2x95x90N).
Calc. C, 73.52; H, 9.65; N, 10.72.
Found: C, 73.14; H, 9.34; N, 10.55.
Ligand 2b
Preparation of the Corresponding Aldehyde
A solution of 13 g (0.04255 mol) of N,N-heptyl-3-amino-phenol, prepared after the procedure described in EP 0356173, in 30 ml chloroform was treated with 6.7 g (0.04255 mol) of phosphorus oxychloride and 12.4 g (0.169 mol) of N,N-dimethyl formamide and worked-up as described for compound 2a. Purification was accomplished by column chromatography a mixture of chlorobenzene/ethyl acetate/ethanol (90:5:5, vol. ratio). 1.78 g (13%) of N,N-heptyl-4-amino-2-hydroxy-benzaldehyde was obtained as a green oily compound. A solution of 0.8 g (0.0024 mol) N,N-heptyl-4-amino-2-hydroxy-benzaldehyde in 1 ml ethanol was treated and worked-up as described for compound 2a. 720 mg (91%) of the ligand was obtained as a brown oil which slowly crystallized when stored at 5xc2x0 C. for three days.
13C NMR (CDCl3): xcex4=14.1 aliph. CH3), 22.6, 27.1, 27.5, 29.2, 31.9, 51.0, 57.7 (aliph. CH2), 98.3, 103.2, 133.0 (tert. Aryl-C), 108.2, 152.1, 166.5 (quart Aryl-C), 164.2 (Cxe2x95x90N).
Calc. C, 76.47; H, 10.79; N, 8.11.
Found: C, 76.18; H, 10.60; N, 7.95.
Ligand 2 c
To a stirred solution of 2 g (0.0121 mol) of 5-dimethylamino-2-hydroxy-benzaldehyde [prepared after Bull. Chem. Soc. Jpn. 51 (1978) 2433] in 6 ml ethanol at 50xc2x0 C. was added dropwise 0.35 g (0.0058 mol) of ethylene diamine. An orange suspension was formed which was stirred at 60xc2x0 C. for 4 h. The suspension was cooled to room temperature, filtered and dried in vacuo at 30xc2x0 C. The pure ligand was obtained as a yellow solid (1.77 g, 87%).
13C NMR (CDCl3): xcex4=45.0 (aliph. NCH3), 60.0 (aliph. CH2), 116.2, 117.2, 119.6 (tert. Aryl-C), 118.4, 144.2, 153.3 (quart Aryl-C), 166.8 (Cxe2x95x90N).
Calc. C, 67.77; H, 7.39; N, 15.81.
Found: C, 67.56; H, 7.35; N, 15.25.
Ligand 2d
To a solution of 2.5 g (0.015 mol) N,N-dimethyl-4-amino-2-hydroxy-benzaldehyde in 7 ml ethanol was added within 2 minutes a solution of 0.82 g (0.00721 mol) of diamino maleic acid dinitrile in 14 ml methanol. The reaction mixture was heated for 5 h at 65xc2x0 C. A brown suspension was obtained which was cooled, filtered and dried to give a brown solid (2.03 g, 70%).
13C NMR (CDCl3): xcex4=40.0 (aliph. NCH3), 110.4, 115.1 (aliph. quart. C), 98.2, 105.8, 133.0 (tert. Aryl-C), 110.4, 115.1, 161.2 (quart Aryl-C), 156.2 (Cxe2x95x90N).
Ligand 2e
A solution of 5.0 g (0.0259 mol) 4-diethylamino-2-hydroxy-benzaldehyde in 12 ml ethanol was treated with 1.66 g (0.0123 mol) of bis-(3-aminopropyl)amine and worked-up as described for ligand 2a. The raw product was dried in high vacuo to give 5.7 g (98%) of a red oil.
13C NMR (CDCl3): xcex4=12.8 (aliph. CH3), 31.1, 44.5, 47.2, 53.6 (aliph. CH2), 98.7, 103.1, 133.2 (tert. Aryl-C), 108.2, 152.2, 169.0 (quart Aryl-C), 162.5 (Cxe2x95x90N).
Calc. C, 68.77; H, 9.00; N, 14.32.
Found: C, 67.09; H, 8.66; N, 13.38 (Substance contains 1.51% water).
Ligand 2f
A solution of 0.81 g (0.00517 mol) 4-chloro-2-hydroxy-benzaldehyde prepared after Beilstein (E IV, vol.8, 223) in 2.5 ml ethanol was treated with 0.29 g (0.00246 mol) trans-1,2-diaminohexane and worked-up as described for ligand 2a. The ligand was obtained as a yellow oil (0.96 g, 100%) which upon standing slowly crystallized.
13C NMR (CDCl3): xcex4=24.1, 32.9 (CH2), 54.6, 72.4 (CH), 117.0, 138.1, 162.0 (quart Aryl-C), 117.2, 118.9 (tert. Aryl-C), 164.0(Cxe2x95x90N).
Calc. C, 61.39; H, 5.15; N, 7.16; Cl, 18.12.
Found: C, 61.50; H, 5.34; N, 7.70; Cl, 17.26.
Ligand 2g
To a stirred solution of 2 g (0.013 mol) 2-hydroxy4-methoxy-benzaldehyde in 10 ml ethanol at room temperature were added at once 579 mg (0.0065 mol) 1,2-diethylamino-2-methylpropane. The solution was heated at 60xc2x0 C. for 3 h and cooled to room temperature. The clear solution was evaporated and dried in high vacuo to give the ligand as a red-brown oil (2.58 g, 100%).
13C NMR (CDCl3): xcex4=25.3(CH3)2Cxe2x80x94), 55.3 (OCH3), 59.2 (aliph, quart. C), 69.2 (NCH2), 101.2, 101.4 (tert. Aryl-C), 106.3, 106.4 (tert. Aryl-C), 112.2, 112.3 (quart Aryl-C), 132.9, 133.1 (tert. Aryl-C), 160.3, 165.6 (Cxe2x95x90N), 163.7, 163.9 (quart. Aryl-C), 165.0, 166.7 (quart. Aryl-C).
Calc. C, 67.39; H, 6.79; N, 7.86.
Found: C, 67.51; H, 6.91; N, 7.69.
Ligand 2h
2 g (0.0103 mol) 4-diethylamino-2-hydroxy-benzaldehyde and 456 mg (0.00517 mol) 1,2-diethylamino-2-methylpropane were treated and worked-up as described for ligand 2g. The ligand was obtained as a red-brown solid (1.9 g, 84%).
13C NMR (CDCl3): xcex4=12.7 (CH3CH2N), 25.4 ((CH3)2Cxe2x80x94), 44.4 (NCH2CH3), 58.4 (quart. C), 68.6 (NCH2), 98.1, 98.6 (tert. Aryl-C), 103.0, 103.1 (tert. Aryl-C), 108.3, 108.4 (quart Aryl-C), 133.1, 133.4 (tert. Aryl-C), 151.6, 151.9 (quart. Aryl-C), 158.9, 164.5 (Cxe2x95x90N), 166.0, 168.4 (quart. Aryl-C).
Calc. C, 71.91; H, 8.74; N, 12.72.
Found: C, 70.88; H, 8.65; N, 12.35.
Ligand 2i
1.21 g (0.006 mol) 4-diethylamino-2-hydroxy-benzaldehyde was dissolved under stirring in 2 ml ethanol at 50xc2x0 C. At this temperature, a solution of 2,3-diamino-2,3-dimethyl-butane (prepared after Beilstein E IV, vol. 4, 1354) in 2 ml ethanol was added within 30 minutes. The reaction mixture was heated to 70 C. for 3 h and stirred at room temperature for another 8 h. The resulting suspension was filtered and the precipitate was washed with cold ethanol and dried in high vacuo to give a brown solid (890 mg, 66%).
13C NMR (CDCl3): xcex4=12.8, 23.0 (CH3), 44.5 (CH2), 63.3 (quart. alipht. C), 98.6, 103.0 133.5 (tert. Aryl-C), 108.2, 152.1, 169.1 (quart. Aryl-C), 158.9 (Cxe2x95x90N).
Calc. C, 72.07; H, 9.07; N, 12.01.
Found: C, 71.78; H, 9.03; N, 11.88.
Ligand 2j
To a solution of 974 mg (0.0045 mol) 2,3,6,7-tetrahydro-8-hydroxy-1H,5H-benzo[ij]quinolizine-9-carboxaldehyde in 30 ml methanol was added a solution of 148 mg (0.0025 mol) ethylene diamine. The reaction mixture was heated under reflux for 1 h. The formed precipitate was filtered and crystallized in 100 ml of methanol to yield 590 mg (29%) of yellow crystals.
13C NMR (CDCl3): xcex4=20.4, 21.3, 22.2, 27.2, 49.8, 50.1, 58.2 (CH2,), 106.8, 107,9, 112,2, 129.0, 146.4, 164.3 (Cxe2x95x90N).
Calc. C, 73.33; H, 7.47; N, 12.22.
Found: C, 73.37; H, 7.54; N, 12.22.
Ligand 2k
A solution of 1.95 9 (0.00714 mol) 8-hydroxy-1,1,7,7-tetramethyljulolidine-9-carboxaldehyde in 60 ml methanol was reacted with 236 mg (0.0393 mmol) ethylene diamine as described for ligand 2j. The precipitate was filtered and washed with methanol to give 1.52 g (75%).
13C NMR (CDCl3): xcex4=28.5 (prim. C), 31.2 (prim. C), 31.7, 32.2, 36.6, 40.1, 47.0, 47.4, 58.9, 108.7, 114.8, 121.6, 127.5), 145.7, 161.2, 165.4 (Cxe2x95x90N).
Ligand 2l
A solution of 5.0 g (0.0355 mol) 2,4-dihydroxy-benzaldehyde in 17 ml ethanol was treated with 1.97 g (0.0169 mol) of trans-1,2-diaminocylohexane and heated at 65xc2x0 C. for 5 h. A yellow suspension was formed which was cooled to 2xc2x0 C. The precipitate was filtered, washed with ethanol and dried to give 5.9 g (99%) of a yellow solid.
13C NMR (DMSO-d6): xcex4=24.9, 33.6 (CH2), 71.3 (CH), 103.3, 107.8, 134.1 (tert. Aryl-C), 112.0, 162.6 (quart. Aryl-C), 164.9 (Cxe2x95x90N)
Ligand 2m
A solution of 5 g (0.025 mol) 4-diethylamino-2-hydroxy-benzaldehyde in 12 ml ethanol was treated with 0.92 g (0.0123 mol) of 1,2-diaminopropane and heated at 65xc2x0 C. for 5 h. The solution was cooled and stirred for 8 h. The solution was concentrated to give 4.68 g (90%) of a brown solid.
13C NMR (CDCl3): xcex4=12.7, 20.3 (CH3), 44.5, 63.8 (CH2), 98.2, 103.1, 133.1 (tert. Aryl-C) 108.3, 151.5, 165.5 (quart. Aryl-C), 162.5 (Cxe2x95x90N).
The following ligands are known compounds. 
These ligands were prepared according to known literature procedures:
All described ligands were transformed into its manganese complexes. The syntheses of these complexes were performed according to the literature as described by E. N. Jacobsen et al. J. Org. Chem., 59 (1994) 1939 or in Patent GB-A-2,296,015. As an example for the standard procedure, the synthesis of the manganese complex 1b is described: To a stirred solution of 667 mg of ligand 3f dissolved in 10 ml of ethanol was added 465 mg manganese-II-acetate-tetrahydrate. The reaction solution was heated at 65-70xc2x0 C. for 4 h. Afterwards, the solution was evaporated and the residue was dissolved in 40 ml of water. The solution were treated with 3.7 g of sodium chloride. The resulting precipitate was filtered and dried in vacuo. The manganese complex was obtained as red-brown powder (820 mg, 86%).